碱金属碳酸盐对煤-CO_2气化反应性影响的研究
摘要
煤气化在高效、清洁利用煤炭资源方面有着非常重要的作用。与其它煤气化过程相比,煤的催化气化工艺具有反应温度低,反应速率快,工艺简单,可定向调节产品气体组成等优越性。
本文以碳含量相当的平朔煤和灵武煤为实验煤样,以Li2CO3、K2CO3、Na2CO3单组分以及相互复合的双组份为催化剂在程序升过程中进行煤的催化气化研究。得出以下主要结论:
1)热重分析表明,三种碱金属碳酸盐Li2CO3、K2CO3、Na2CO3均对平朔煤、灵武煤显示出良好的催化活性,使气化反应速率增大,气化反应终温降低,平朔煤、灵武煤添加10%催化剂时分别降低300℃、400℃左右,对平朔煤的催化活性顺序为Li2CO3>K2CO3>Na2CO3;
2)双组份复合催化剂对平朔煤、灵武煤也表现出良好的催化活性,并进行了双组分复合催化剂较佳配比的选择,平朔煤添加Li2CO3-K2CO3的摩尔比为9:1, 1:7和7:1时较佳,灵武煤添加Li2CO3-K2CO3的摩尔比为7:1和3:1时较佳;平朔煤、灵武煤添加Li2CO3-Na2CO3的最佳摩尔比为9:1,双组份催化剂的催化活性优于单组分催化剂,但并不是任意复合催化剂的活性都优于单组分。
3)催化剂负载量对煤催化气化有显著影响,随着催化剂量的增加其催化活性增大,但催化剂用量过高不能充分发挥其催化作用,而且造成原料的浪费,选择出催化剂最佳负载量为10%.
4)通过对气化后气相色谱数据分析,认为催化剂对平朔煤热解阶段H2、CH4、C2-C4的释放起到了一定的催化作用,对气化阶段CO的释放催化作用显著,CO的释放量随气化温度的升高呈现增大的趋势,且CO的释放温度较原煤降低了300℃左右,与热分析实验结果具有一致的趋势。
Coal gasification has an important function on high efficient and clean utilization of coal resource. Compared with other coal gasification technologies, coal catalytic gasification technology has the advantages of lower reaction temperature, higher reaction speed, more simple technology and regulable components of gaseous production.
Pingshuo and Lingwu raw coal, which has the same carbon content, were used in this text. The single or mixture of binary Li2CO3, K2CO3 and Na2CO3 were selected as catalysts of coal gasification during TGA temperature programme experiment. The main conclusions are as fllowing:
1) The TGA analysis show that Li2CO3、K2CO3 and Na2CO3 all have favorable catalytic activity to Pingshuo and Lingwu raw coal, and make increase the speed and reduce the final temperature of gasification reaction. The final temperatures of gasification reaction reduce about 300℃and 400℃respectively for Pingshuo and Lingwu raw coal when 10% catalysts was loaded. The order of catalytic activity to Pingshuo raw coal gasification is Li2CO3 > K2CO3 > Na2CO3.
2) Binary catalysts show also better catalytic activity to Pingshuo and Lingwu raw coal gasification than that of single alkali carbonate, the better ratio of binary catalysts were selected. The best mole ratio of Li2CO3 and K2CO3 is 9:1, 1:7 and 7:1 to Pingshuo coal, and is 7:1 and 3:1 to Lingwu coal. The best mole ratio of Li2CO3 and Na2CO3 is 9:1 to Pingshuo and Lingwu coal. Comparing the single and binary catalysts, the latter present the higher catalytic activity. Not that the activity of arbitrary binary catalyst were superior to single catalyst.
3) the loading quantity of catalysts have an remarkable influence to the coal gasification. With the increase of catalytic dose the catalytic activity increase also. But the catalyst cannot give full play when the quantity too large and cause of materials waste. The best loading quantity of the catalysts in coal is 10% to Pingshuo and Lingwu coal.
4) According to the products analysis of Pingshuo coal gasification reaction, the catalysts has definite effect on the release amount of H2、CH4、C2-C4. and it has an remarkable influence on the release of CO, which the initial release temperature is reduced about 300℃in accordance with the result of TG study.
本文以碳含量相当的平朔煤和灵武煤为实验煤样,以Li2CO3、K2CO3、Na2CO3单组分以及相互复合的双组份为催化剂在程序升过程中进行煤的催化气化研究。得出以下主要结论:
1)热重分析表明,三种碱金属碳酸盐Li2CO3、K2CO3、Na2CO3均对平朔煤、灵武煤显示出良好的催化活性,使气化反应速率增大,气化反应终温降低,平朔煤、灵武煤添加10%催化剂时分别降低300℃、400℃左右,对平朔煤的催化活性顺序为Li2CO3>K2CO3>Na2CO3;
2)双组份复合催化剂对平朔煤、灵武煤也表现出良好的催化活性,并进行了双组分复合催化剂较佳配比的选择,平朔煤添加Li2CO3-K2CO3的摩尔比为9:1, 1:7和7:1时较佳,灵武煤添加Li2CO3-K2CO3的摩尔比为7:1和3:1时较佳;平朔煤、灵武煤添加Li2CO3-Na2CO3的最佳摩尔比为9:1,双组份催化剂的催化活性优于单组分催化剂,但并不是任意复合催化剂的活性都优于单组分。
3)催化剂负载量对煤催化气化有显著影响,随着催化剂量的增加其催化活性增大,但催化剂用量过高不能充分发挥其催化作用,而且造成原料的浪费,选择出催化剂最佳负载量为10%.
4)通过对气化后气相色谱数据分析,认为催化剂对平朔煤热解阶段H2、CH4、C2-C4的释放起到了一定的催化作用,对气化阶段CO的释放催化作用显著,CO的释放量随气化温度的升高呈现增大的趋势,且CO的释放温度较原煤降低了300℃左右,与热分析实验结果具有一致的趋势。
Coal gasification has an important function on high efficient and clean utilization of coal resource. Compared with other coal gasification technologies, coal catalytic gasification technology has the advantages of lower reaction temperature, higher reaction speed, more simple technology and regulable components of gaseous production.
Pingshuo and Lingwu raw coal, which has the same carbon content, were used in this text. The single or mixture of binary Li2CO3, K2CO3 and Na2CO3 were selected as catalysts of coal gasification during TGA temperature programme experiment. The main conclusions are as fllowing:
1) The TGA analysis show that Li2CO3、K2CO3 and Na2CO3 all have favorable catalytic activity to Pingshuo and Lingwu raw coal, and make increase the speed and reduce the final temperature of gasification reaction. The final temperatures of gasification reaction reduce about 300℃and 400℃respectively for Pingshuo and Lingwu raw coal when 10% catalysts was loaded. The order of catalytic activity to Pingshuo raw coal gasification is Li2CO3 > K2CO3 > Na2CO3.
2) Binary catalysts show also better catalytic activity to Pingshuo and Lingwu raw coal gasification than that of single alkali carbonate, the better ratio of binary catalysts were selected. The best mole ratio of Li2CO3 and K2CO3 is 9:1, 1:7 and 7:1 to Pingshuo coal, and is 7:1 and 3:1 to Lingwu coal. The best mole ratio of Li2CO3 and Na2CO3 is 9:1 to Pingshuo and Lingwu coal. Comparing the single and binary catalysts, the latter present the higher catalytic activity. Not that the activity of arbitrary binary catalyst were superior to single catalyst.
3) the loading quantity of catalysts have an remarkable influence to the coal gasification. With the increase of catalytic dose the catalytic activity increase also. But the catalyst cannot give full play when the quantity too large and cause of materials waste. The best loading quantity of the catalysts in coal is 10% to Pingshuo and Lingwu coal.
4) According to the products analysis of Pingshuo coal gasification reaction, the catalysts has definite effect on the release amount of H2、CH4、C2-C4. and it has an remarkable influence on the release of CO, which the initial release temperature is reduced about 300℃in accordance with the result of TG study.
引文
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[16] Yaw D.Yeboah, Xu Yong, Atul Sheth, et al. Catalytic gasification of coal using eutectic salts:identification of eutectics[J]. Carbon, 2003, 41: 203-214
[17]李松栋,庞宪勇,鲍卫仁等.煤在新型等离子体反应器内的气化[J].太原理工大学学报, 2004, 35(5): 510-513
[18] Muller R, Zedtwitz P V, Wokauna A. Kinetic investigation on steam gasification of charcoal under direct high-flux irradiation[J]. Chemical engineering Science 2003, 58(5): 111-119
[19]金会心,王华.聚光太阳能加热昭通褐煤的气化试验研究[J].燃料化学学报, 2001, 29(6): 548-552
[20] Yoshitomo I, Motoo F. Coal gasification systerm using nuclear heat for Ammoniaproduction[J]. Applied Energy, 2000, 67: 395-406
[21]倪建军,梁钦锋,周志杰等.气流床煤气化辐射废锅内多相流动与传热[J].化工学报, 2009, 12, 60(12): 2997-3005
[22]任永强,许世森,夏军仓等.干煤粉加压气流床气化试验研究[J].热能动力工程, 2007, 22(4): 431-434
[23]高旭霞,郭晓镭,龚欣.气流床煤气化渣的特征[J].华东理工大学学报(自然科学版)2009, 35(5): 677-683
[24]张泽凯,王黎,刘业奎等.金属复合催化剂对煤气化的暂态动力学研究[J].燃料化学学报, 2004, 32(3): 263-267
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